Thermal standard cell



y 6, 1952 T. A. RICH El AL 2,595,814

THERMAL STANDARD CELL Filed April 6, 1949 2 SHEETS-SHEET 1 COPNIQ COLD DETECTOR JUNCTION AND 0 AMPLIFIER Fig. 2.

Lil n: I I E I m I D. 1 a i I l I I P I p I 1 PRESSURE (mm) Inventors:

Theodore A. Rich,

John E. Bigelovv, by WW5. 4W2

The lr" Attorney.

y 6, 1952 T. A. RICH |=:r AL 2,595,814

THERMAL STANDARD CELL Filed April 6, 1949 2 SHEETS-SHEET 2 Fig. 4.

Inventors: Theodore A. Rich, John E. Si ge-low,

b fie fi/ Then Attorney.

Patented May 6, 1952.

UNITED STATES PATENT OFFICE THERMAL STANDARD CELL Theodore A. Rich and John E. Bigelow, Schenectady, N. Y., assignors to General Electric Company, a corporation of New York Application April 6, 1949, Serial No.-85,-888

1 Claim. -1

Our invention relates to electrical reference devices and more particularly to a new and improved form of standard cell.

In electrical apparatus for precisely measuring or controlling physical quantities, such as temperatures and the like, it is frequently desirable to make use of a reference voltage as a standard of comparison with an unknown signal voltage representing a quantity being measured. This is particularly the casewhen such a signal voltage is-of relatively small magnitude and of necessity must be amplified to be conveniently utilized.

A typical apparatus of the type mentioned is an indicating and recording device wherein a relatively feeble signal voltage, from a thermocouple or the like, is compared with a reference voltage. The difference of the signal and reference voltagesgis utilized, through the mechanism of an automatic follow-up arrangement, such as a motor-driven slide-wire device, to position a pointer and recording stylus, thereby causing the value of the-measured quantity to be indicated and recorded.

A suitablereference voltage may be obtained by theme of a so-called standard cell. Such a device is commonly understood to include a source of voltage, calibrated to a high degree of accuracy, having aparticularly constant and reliable voltage output under specified physical conditions, .such as ambient temperatures and load burden imposed upon the cell. In modern applications, industrial and otherwise, it is especially desirable that standard cells be capable of withstanding, without harmful effect, conditions of operation to which associated equipment may besubjected.

Such cells preferably are capable of withstanding freezing and other extremes of ambient temperatures; conditions of overloading; mechanical abuse incurred in transportation from one point to another; and such other abnormal conditions as may reasonably be experienced in common use, without material change of calibration. In certain applications it is desirable to draw from such cells relatively substantial loads for considerable periods of time. Furthermore, it is advantageous to be able to store such cells for considerable periods of time with assurance that the calibrations thereof would not be materially affected. In addition since applications requiring the vuse of standard cells are large in number, it is desirable that such cells be of simple design and construction to permit ease of manufacture and low cost to the user.

Accordingly, it is an object of our invention to provide a new and. improved form of standard cell.

It is another object of ourinvention to provide a standard cell which may be subjected to a relatively wide range of temperatures, and which may be safely transported from point to point, without loss of accuracy or material change. of calibration.-

It is a further object of our invention to provide a new and improved standard cell which may be substantially'loaded'for a considerable period of time, or subjected to overload conditions, without loss of accuracy or material change of calibration.

It is a still further object of our invention to provide a new and improved standard cell which possessesa high degree of accuracy and which is simple in construction, reliable in operation, and inexpensive to manufacture.

In its broadest aspect, our invention makes use of the difference in boiling temperatures of a pair of liquids of particular composition, such difference for certain selected liquids being substantially constant over a considerable range of ambient pressures. According to one embodiment of our invention, We provide suitable vessels for boiling a pair of such liquids by the use of associated heating devices, preferably electrical heating elements submerged therein. To sense the temperatures of the boiling liquids or the saturated vapors thereof, we provide thermo-electric devices, preferably thermocouples, connected in series relation to have an output voltage proportional to the difference of the boiling temperatures.

Thus, our apparatusprovides a source of voltage which is dependent only on the boiling temperatures of the liquids used therein, and the voltage output characteristics of the associated sensing devices. Since, as is well known, the boiling temperatures of specified liquids, at particular pressures, are highly stable, and the voltage output characteristics of particular types of thermccouples may be made stable within extremely .narrowiimits, the apparatus of our invention providesa voltage output which is likewise exceedingly stable and which may be calibrated to a high degree of accuracy.

A particular feature of our invention, especially useful in applications wherein measure- .mentsare made'utilizing relatively feeble signal voltages obtained from thermocouples or the like,

is the provision ofa standard voltage of theorder of magnitude of such measured voltages. By having standard and measured voltages approximately equalin magnitude, the use of voltage dividers and the like, which are frequently employed with voltage standards providing relatively large voltages with respect to measured voltages, is generally unnecessary.

For a better understanding of our invention, together with further objects and advantages thereof, attention is now directed to the following description and the figures of the accompanying drawings, and also to the appended claim, in which the features of my invention believed to be novel are set forth.

Fig. 1 represents diagrammatically a temperature measuring apparatus of the type having a motor-driven follow-up mechanism, including as a standard cell reference element a preferred embodiment of our invention; Fig. 2 represents a modification of the embodiment shown in Fig. 1; Fig. 3 graphically represents certain physical characteristics of our invention; Fig. 4 represents diagrammatically a current standard provided with compensation for variations in ambient pressure; and Fig. 5 represents a voltage standard also provided with compensation.

Referring now to Fig. l of the accompanying drawing, there is shown an electrical measuring apparatus, the function of which is to measure a temperature and record the value thereof on a strip chart. The apparatus comprises generally a sensing element I, such as a thermocouple, and an associated cold junction compensating device 2, a detector and amplifier 3, a slide-wire device 4, a reversible motor 5, a chart mechanism 8, and a reference voltage device or standard cell, which may be designated as a whole by numeral I. With the exception of standard cell 1, which is the subject of the present invention and which will be dealt with hereinafter, the apparatus is of a conventional type well known in the art.

Thermocouple I is represented diagrammatically as being arranged to sense the temperature of a substance 8 flowing through a pipe 9. One terminal of thermocouple I is connected to one terminal of compensating device 2 which may be, for example, a jar containing a mixture of ice and water. The other terminal of compensating device 2 is connected to end terminal II of slide-wire 4. The other terminal of thermocouple I is connected to one of a pair of terminals of an input circuit III of detector and amplifier 3, while the other terminal of input circuit I8 is connected to sliding contact I2 of slide-wire 4. An output circuit I3 of detector and amplifier 3 is connected to the terminals of reversible motor 5, which may be of the split-series field type. The rotating shaft I4 of motor 5 is arranged mechanically to drive sliding contact I2 of slide-wire 4 and move stylus I5 of chart mechanism 6. In the operation of the system as thus far described, a voltage V1 proportional to the temperature of substance 8 surrounding thermocouple I is produced across the series-connected combination of thermocouple I and compensating device 2.

A reference voltage V2 is impressed by standard cell I across the end terminals II and I6 of slide wire 4. A voltage V3, comprising a fractional portion of voltage V2, exists across points I I and I2 of slide-wire 4. Voltages V1 and V3 are connected in series relation causing the voltage impressed on input circuit ID of detector and amplifier 3 to be the difference of voltages V1 and V3. More particularly, when voltages V1 and V: are equal in magnitude the voltage impressed across input circuit III is zero. The internal arrangement of detector and amplifier 3 is such that motor 5 is energized and. caused to rotate in such a manner that sliding contact I2 seeks at all times a position causing the voltage impressed on input circuit III to be zero. In other words, the apparatus comprising thermocouple I, compensating device 2, detector and amplifier 3, slide wire 4, and motor 5 functions as a so-called null system. The output shaft of motor I4, in positioning sliding contact I2 also positions stylus I5 to record the value of the temperature sensed by thermocouple I.

It should be understood that the elements of the apparatus thus far described are of conventional type and do not constitute a part of the present invention. The discussion of the apparatus comprising the elements mentioned is included primarily as an aid in the understanding of our invention, which resides, in the present embodiment, in a new and improved standard cell reference device I, the function of which is to provide reference voltage V1, as will be presently explained.

Referring now to the bracketed portion of Fig. 1, designated by numeral 1, there is shown an electrical reference device, which we have chosen to call a standard cell. We provide a pair of vessels I I and I8 which may be vacuum flasks having inner walls I9 and outer walls 28, separated by substantially evacuated space 2I. Vessels I1 and I8 are suitably arranged to contain in cavities 22 and 23 thereof, a pair of liquids 24 and 25 having, as a primary characteristic, different boiling temperatures. The manner of choosing the particular liquids employed will be subsequently described. Associated with vessels I1 and I8, respectively, are a pair of reservoirs 26 and 21, arranged to discharge into a pair of intermediate vessels 28 and 29, the latter being connected to vessels I1 and I8, respectively, by means of tubular passags 30 and 3 I. Passageways 38 and 3| enter cavities 22 and 23 of vessels I1 and I8 at points beneath the surfaces of liquids 24 and 25. Portions of liquids 24 and 25 are contained in cavities 22 and 23, while other portions are contained in reservoirs 26 and 21, vessels 28 and 29 and passageways 38 and M. It will be understood that combinations of elements 26, 23 and 38, and 21, 29 and 3|, function in the manner of storage reservoirs of the type commonly employed in stock watering devices and the like, in that a relatively constant level of liquid is maintained in vessels 28 and 29 and cavities 22 and 23. Since reservoirs 26 and 21 are sealed by the liquids contained in vessels 28 and 29, partial vacuums existing in reservoirs 26 and 21 tend to prevent escape of liquids 24 and 25 therefrom until the openings thereof are uncovered by lowering of the liquid levels in vessels 28 and 29 to allow gases to enter reservoirs 26 and 21. The entrance of such gases relieves, to some extent, the partial vacuums existing in reservoirs 26 and 21, permitting additional amounts of liquids 24 and 25 to escape therefrom into vessels 28 and 29, thereby increasing the levels of liquids 24 and 25 in vessels 28 and 29 and vessels I1 and I8. The rate of fiow of liquids 24 and 25 from vessels 28 and 29 to vessels I1 and I8, respectively, may be controlled by suitably restricting passageways 30 and 3I.

To effect boiling of the portions liquids 24 and 25 contained within cavities 22 and 23 of vessels II and I8, we provide a pair of heating devices which are represented in Fig. 1 as electrical resistance elements 32 and 33 submerged respectively within liquids 24 and 25. Heatin elements '32 and 33* are supplied with electrical energy froma suitable current source 34 through variable resistances 35' and 36 respectively, the latter being employed to adjust the degree of heating of elements32 and 33;

It will be understood that when boiling occurs within cavities 22 and 23 saturated vapors of liquids M ami 25 will be formed therewithin abovethe liquid surfaces and, further, that such vapors will be expelled from the vessels with subsequent loss of liquid. While aspreviously explained, liquids 24 and 2.5 will be replenished from other portion's thereofcontained. in reservoirs- 26 and 21, --it is desirablefrom the standpoint of ultimate replacement of the liquid supplies, to eifect'reduction of the rate of liquid loss attributableto expelled vapors, andto reclaim as much of the lost liquidsas possible. Accordingly, a pair of condensing devices 31 and 38 is provided, condensers 31 and 38 being attached respectively to the open portions or mouths of vessels I1 and I8. Condensers 3? and 38 may take: the form of a plurality of convolutions of a'material, such as metal, having a relatively high degree of thermal conductivity. Condensers 31' and 38 are provided with passageways therethrough terminating in openings 39 and 40 which are arranged to be subjected to substantially identical ambient pressures. By the use of condensers 31 and 38 vapors created by boiling of liquids 24 and 25 will, upon contact with the relatively cooler inner surfaces of condensers 37 and 38, tend to condense and return to a liquid state, and be drawn back by gravity forces to the boiling portions of the respective liquids, thereby tending to reduce the. rate of liquid loss.

To sense the temperatures of the saturated vapors in the immediate vicinities of boiling liquids 24 and 25, the vaporous regions'corresponding thereto being represented by numerals 24" and 25" respectively, we provide a pair of thermo-electric devices which are represented in the present embodiment as a pair of thermocouples 4! and 42 located in vaporous regions 24' and 25. Depending upon the degree of sensing accuracy desired a number of different arrangements of thermocouples M and 42 may be employed. A preferred arrangement in cases where a relatively high degree of accuracy is desired is shown in Fig. 1. In particular, the leads or connections to thermocouples 4| and 42 are. brought in beneath the surfaces of liquids 24 and 25 so arranged that when thermocouples 4| and .2 are suitably located in vaporous regions'24 and 25', the leads of thermocouples H and 42 are submerged in boiling liquids 24 and 25. The eiTect of submerging the leads of thermocouples 4| and 42 is to provide thermal "guards to maintain such leads at temperatures very close to the actual temperatures being sensed in vaporous regions 24' and 25. In this manner, high temperature gradients are avoided in the leads to thermocouples 4| and 42 which would tend to impart false indications of the temperatures being sensed.

In the arrangement fif'Fig. l, we provide, additionally, a pair of wicks 43 and 44 arranged to contact thermocouples 4i and 42, respectively, and to extend beneath the surfaces of boiling liquids 24 and 25. By the use of wicks 43 and 44, which are preferably formed of a pliable, absorbent material such as cotton, thin films of liquid are conveyed to thermocouples 4i and 42 to provide a wetting action on the surfaces thereof, thereby causing the temperature sensing 6 characteristics of thermocouples l l and. tube more rapid and reliable, than would otherwi'se be the case.

It will-be understood that conditionsof superheating" may exist in boiling liquids '24 and: 25 causing the actual temperatures therein to differ, in certain cases by several degrees, from the true boiling temperatures thereof. By placing ther mocouples' 4| and t2 in vaporous regions 24' and 25, and by the use of wicks 43 and 46, we have found that the true boiling temperatures of liquids'2 4 and 25 maybe sensed and errors introduced' by accidental superheating may be eliminated.

In cases wherelesser degrees of accuracy. are required, it may be desirable from the standpoint of simplicity and economy of construction. to locate sensing elements, such: as thermocouples ll. and 42, beneath thesurfaceof boiling liquids such as liquids 24 and25, and thus to sensethe actual temperatures therein without regard to accidental superheating. Such. an arrangement isshownin. Fig. 2, wherein a single vessel and associated elements, similar to and having the same numerals as one of the groups of elements of Fig. l, are shown. In particular, it Will be seen that thermocouple 4| is located beneath the surface of boiling liquid 24 as previously described. With this arrangement a wick, such as wick 43 of Fig. l, is unnecessary since excellent thermal transfer characteristics are obtained by the intimate contact of thermocouple 4| and liquid 24.

The theoretical considerations on which our invention is based are graphically represented in Fig. 3, wherein curves 45 and 46 represent the boiling temperature vs. ambient pressure relationships of liquids 22 and 25 of Fig. 1, designated. asv A and B, respectively. It is'well known that such temperature-pressure characteristics are very nearly linear functions for small pressure changes and as such are represented graphically by straight lines having the general mathematical expression T=To+K(PPo), wherein T is the boiling temperature of a particular liquid ata particular pressure P with respect to the standard boiling temperature To thereof at a standard pressure Pu, and K is a constant temperature-pressure coefficient, the value of which depends upon the particular liquid employed. Ideally liquids A and B are selected to have identical constant KA and KB in which case the straight lines 65 and 46 of Fig. 3 have a parallel relationship.

In particular, in Fig. 3, curves 45 and 45 are assumed to be essentially straight lines and any tendency thereof to depart from true parallelism is ignored. For the sake of illustration a number of values of ambient pressure are indicated in Fig. 3 as P0, P1, and P2. The boiling temperatures for liquids A and B corresponding to a reference pressure P0 are represented in Fig. 3 as points To andxTo' on curves 45 and 56 respectively, and the difference of To and To is indicated as'ATo. Theboiling temperatures of liquids A and B at other ambient temperatures P1 and P2 are similarly indicated as T1 and T1 and T2 and T2, the differences corresponding thereto being indicated by ATI and ATz respectively. Since, as previously assumed, straight lines 45 and is have substantially identical slopes, it follows that ATo and ATi and ATz are substantially identical quantities, which is a mathematical manner of indicating that the difference in boiling temperatures of a pair of liquids having substantially equal 7 4. temperature-pressure coefiicients are substantially constant with variable ambient pressure conditions.

While, as previously indicated, it is desirable to use a pair of liquids having identical temperature-pressure coefficients, it may be necessary to use a pair of liquids having slightly difierent temperature-pressure coefiicients. In certain applications where a high degree of accuracy is not essential it may be possible to tolerate a variation in the difierence of boiling temperatures with changing ambient pressure. However, in other cases, it may be desirable to provide compensating devices which permit the attainment of a higher degree of accuracy. We therefore provide, in the following modifications of the general embodiment described above, arrangements whereby such compensation may be effected.

It will be helpful in the understanding of our invention to examine the temperature-pressure relationships for a pair of liquids having slightly diilerent temperature-pressure coefficients. For example, let it be assumed that liquid A is water, the temperature-pressure relationship thereof being represented by the expression wherein TA is the boiling temperature of water expressed in degrees centigrade for a particular ambient pressure P expressed in millimeters of mercury. Let it be assumed that liquid B is o-toluidine having a temperature-pressure relationship TB=199.'7+0.58(P'760) wherein similar characters are employed. Curve 45 in Fig. 3 represents the temperature-pressure characteristic of liquid A, assumed to be water, while curve 46 represents the characteristic of liquid B, assumed to be o-toluidine. It will be understood that for the assumed liquids curves 45 and 4B in Fig. 3 are not parallel lines but have a degree of divergence, since, as previously explained, the temperature-pressure coefficients of the assumed liquids A and B are not identical. Therefore, the difference in boiling temperatures of liquids A and B represented as ATo, AT1, and ATz, are not equal for corresponding pressures P0, P1, and P2, but may be represented by the relationship AT=99.7+0.22 (P760) Accordingly, a change in pressure P of approximately 5.0 mm. gives an error of approximately 0.1 percent in voltage output of the thermocouple devices 4| and 42 shown in Fig. 1.

In Fig. 4, we show an arrangement to compensate for the variation of AT in a system making use of our invention as a current standard. The elements represented in Fig. 4 are the same as those represented in Fig. 1 with the exception that a plurality of thermocouple devices grouped in arrangements commonly known as thermopiles and designated by numerals 4| and 42' in Fig. 4, are substittued for thermocouples 4| and 42 shown in Fig. 1. Thermopiles of the type shown may be conveniently used when it is desired to secure a greater electrical voltage output than is provided by a single pair of thermocouples.

Thermopile 4| is arranged to sense the boiling temperature of liquid A, While thermopile 42' is arranged to sense the boiling temperature of liquid B. Thermopiles 4| and 42 are connected in series relation in a manner to provide a source of potential responsive to the difference of the temperatures sensed by thermopiles 4| and 42'.

To provide compensation for the difierence in temperature-pressure coefiicients of liquids A and B, we make use of the resistance-temperature characteristic of a resistance, designated by numeral 41. Resistance 41 is positioned in proximity to thermopile 42 so that both resistance 41 and thermopile 42' are subjected to substantially identical temperatures.

In the arrangement of Fig. 4, thermocouples 4| and 42 are connected in a series with resistance 41 and an impedance comprising an-indicating instrument 48. The electrical voltage developed in thermopiles 4 and 42 due to heating of thermopiles 4| and 42' by boiling liquids A and B causes a current to flow in resistor 41 and instrument 48.

With the assumed chosen liquids if the ambient pressure P is increased, it will be seen from the relationship given above for the difference AT in boiling temperatures of liquids A andB, that such difi'erence becomes greater with increasing pressure. As is well known, the voltage output of a pair of thermopiles, such as thermopiles 4| and 42', is approximately directly proportional to the temperature diilerence sensed thereby. Accordingly, in the circuit comprising thermopiles 4| and 42, resistance 41, and instrument 48, increasing voltage output of thermopiles 4| and 42 tends to cause an increase in the current flowing in the circuit. However, by choosing for resistance 41, a resistance material having a suitable resistance-temperature coeficient and by subjecting resistance 41 to the boiling temperature of liquid B, resistance 41 may be made to increase at a rate comparable to the rateof increase of AT with increase of ambient pressure P. For the assumed liquids, water and o-toluidine, a resistance material having a resistance-temperature coefiicient of 0.004 ohm per ohm per degree centigrade provides very nearly exact compensation.

In Fig. 5 there is shown an arrangement to compensate for the variation of AT in an arrangement making use of our invention as a voltage standard. The elements represented in Fig. 5 are the same as those represented in Fig. 1. In the circuit of thermocouples 4| and 42, we provide a plurality of resistances, designated as 49, 50, and 5|, for the purpose of compensating the output voltage V from thermocouples 4| and 42 for variations in AT with variations in ambient pressure P. A circuit is formed comprising thermocouples 4| and 42, resistance 49 and the parallel combination of resistances 50 and 5|. Resistances 49 and 50 are formed of a resistance material having an exceedingly small resistance-temperature coefficient, hence resistances 49 and 5|] are substantially constant over a wide range of temperatures. Resistance 5|, however, is formed of a material having a negative resistance-temperature coefiicient, such as a thermistor, and is subjected to substantially the same temperature as thermocouple 42. Thus as AT increases, due to an increase in ambient pressure P the voltage output of thermocouples 4| and 42 likewise increases, tending to cause an increase in the current flow in resistances 49, 50 and 5|. However, with increasing temperature the value of resistor 5| tends to decrease while the values of resistances 49 and 50 remain constant. Therefore, the voltage across the parallel combination of resistances 5|] and 5| may be made to remain constant by suitable choice of values of resistances 49, 5|] and 5|, and by the choice of a material having a suitable resistance-temperature coeflicient for resistance 5|.

Typical satisfactory resistance values, using for resistance 5| a material having a negative resistance-temperature coefiicient of 0.03 ohm per ohms per degree centigrade, are as follows: Resistance 49, 10 ohms; resistance 50, 100 ohms; resistance 5|, 62.6 ohms.

It will be understood that compensation for variation of output voltage in the arrangements of both Figs. 4 and 5, due to variations in boiling temperatures, is provided by the use of temperature-responsive resistance devices. In each case such a resistance device is arranged to sense one of the boiling temperatures; and to cause an increase or decrease in circuit resistance as required by the particular arrangement employed. Errors which may be introduced in such arrangements by variations in the temperatures to which the temperature-sensing elements such as thermocouples 4i and 42 may be subjected, may be compensated in general by suit ably proportioning the values of circuit components, such as resistors 49, 50 and 5 I It is also possible to employ thermocouples which do not have an exact linear relationship between voltage and temperature which has been assumed herein. In some thermocouples this variation tends to be self-compensating with the particular liquids used. In any event the methods shown herein can be applied to compensate for such errors.

While we have shown and described a preferred embodiment of our invention, it will be understood that our invention may well take other forms and we, therefore, aim in the appended claim to cover all such changes and modifications as fall within the true spirit and scope of our invention.

What we claim as new and desire to secure by Letters Patent of the United States is:

In combination, a pair of vessels having the inner portions thereof exposed to the atmosphere, a pair of liquids having different boiling temperatures, said liquids being separately contained in said vessels and subjected to varying pressures, said liquids having substantially parallel vapor pressure vs. temperature characteristics at atmospheric pressures} electrical heating means for maintaining said liquids at said boiling temperatures, means including a pair of electrical devices for sensing said temperatures, said sensing devices being arranged to have an output voltage responsive to the difierence of said'boiling temperatures, means comprising a temperature-responsive resistance arranged to sense one of said temperatures, said resistance being connected with said devices to maintain said output substantially constant for variations in said pressure.

THEODORE A. RICH. JOHN E. BIGELOW.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS 

